MXPA00000010A - Thermosetting aqueous compositions - Google Patents

Abstract

Thermosetting aqueous compositions comprising a polymerizate component bearing carboxyl groups and optionally a hydroxyalkylated amine, and the use thereof as binding agents for mouldings.

Description

THERMOCURABLE AQUEOUS COMPOSITIONS The present invention relates to thermosetting aqueous compositions consisting of a polymeric component containing carboxyl and a hydroxyalkylated amine and their use as binders for formed articles. The solidification or consolidation of fibrous leaf-like structures such as fibrous non-wovens, articles formed as fibreboard or cardboard panels, etc., are often made chemically using a poly-binder. To increase strength, especially resistance to wetting and thermostability, it is common to use binders whose crosslinkers produce formaldehyde. However, this carries the risk of formaldehyde emissions. To avoid formaldehyde emissions, numerous alternatives have already been proposed for the binders known to date. For example, US-A-4, 076, 917 describes the binders whose cross-linkers contain β-hydroxyalkylamides and polymers containing carboxylic acid or carboxylic anhydride. The molar ratio of carboxyl to hydroxyl is preferably 1: 1. A disadvantage is the relatively complex preparation of the β-hydroxyalkylamides.

EP-A-445 578 discloses sheets prepared from finely divided materials, such as glass fibers, in which mixtures of polycarboxylic acids of high molecular mass and polyhydric alcohols, alkanolamines or polyfunctional amines act as binders. The polycarboxylic acids of high molecular mass described are polyacrylic acid and the copolymers ethyl methacrylate-n-butylacrylate-methacrylic acid and methyl methacrylate-methacrylic acid. The polyhydric alcohols or alkanolamines used are 2-hydroxymethyl-l, 4-butanediol, trimethylolpropane, glycerol, poly (methyl methacrylate-co-hydroxypropyl acrylate), diethanolamine and triethanolamine. However, the water resistance of the resulting sheets is unsatisfactory. EP-A-583 086 discloses aqueous binders without formaldehyde to produce continuous fiber materials, especially continuous glass fiber materials. The binders consist of polycarboxylic acid with at least two carboxyl groups with or without anhydride groups. In particular, polyacrylic acid is used. The binder also contains a polyol, for example glycerol, bis [N, N-di (β-hydroxyethyl) dipamide, pentaerythritol, diethylene glycol, ethylene glycol, gluconic acid, β-D-lactose, sucrose, polyvinyl alcohol, diisopropanol , 2- (2-aminoethylamino) ethanol, triethanolamine, tris (hydroxymethylamino) methane and diethanolamine. These binders require a phosphorus-containing reaction accelerator to achieve sufficient strengths of the glass fiber non-wovens. It is mentioned that an accelerator of the reaction of this kind can only be absent if a highly reactive polyol is used. The β-hydroxyalkylamides are mentioned as highly reactive polyols. EP-A-651 088 describes the corresponding binders for cellulose fiber substrates. These binders necessarily include a reaction accelerator containing phosphorus. EP-A-672 920 discloses formaldehyde-free binders, impregnation compositions or coating compositions containing at least one polyol and a polymer of which from 2 to 100% by weight is represented by an ethylenically unsaturated acid or an acid anhydride comonomer. The polyols are substituted triazine, triazinetrione, benzene or cyclohexyl derivatives, the polyol radicals always being in position 1, 3 and 5 of these rings. Despite a high drying temperature, the wet tear strengths achieved by these binders on glass fiber nonwovens are low. In comparative experiments, crosslinkers containing amines and also mainly linear polyols were tested. It is mentioned that the crosslinkers containing amines have a flocculating effect and that the mainly linear polyols give rise to weaker cross-linking compared to the cyclic polyols. DE-A-22 14 450 describes a copolymer composed of from 80 to 99% by weight of ethylene and from 1 to 20% by weight of maleic anhydride. The copolymer in powder form or dispersion in an aqueous medium is used together with a crosslinker, for surface coating. The reticular used is a polyalcohol containing amino. However, to carry out the crosslinking it is necessary to heat the system to 30'0 ° C. EP-A-257 567 discloses a polymer composition obtainable by emulsion polymerization of ethylenically unsaturated msnomers, such as olefins, vinylaromatic compounds, α, β-ethylenic unsaturated carboxylic acids and their esters, ethylenically unsaturated dicarboxylic anhydrides and vinyl halides . To influence the flow properties of the polymeric composition, a soluble or dispersible resin in water or alkali with a number average molecular weight of from about 500 to about 20,000 is added during the polymerization. The resin is composed of olefins, vinylaromatic compounds, α, β-ethylenically unsaturated carboxylic acids and the esters thereof or ethylenically dicarboxylic anhydrides unsaturated Ammonium hydroxide is indicated as the alkaline medium in which the resin will be soluble or dispersible. The composition can be used to produce formaldehyde-free coatings on wood substrates. EP-A-576 128 describes adhesive compositions that can re-form pulp and that consist of an acid-rich polymer component and a low-acid polymer component. The polymer component rich in acid is based on a monomer mixture of from 40 to 95% of an alkyl acrylate or ethacrylate and from 5 to 60% of an ethylenically unsaturated acid, such as acrylic or methacrylic acid. The polymer component low in acid is based on a mixture of monomers from 90 to 100% of an acrylate or alkyl methacrylate and from 0 to 10% of an ethylenically unsaturated acid. The compositions are prepared by aqueous emulsion polymerization, with the acid-rich polymer component being polymerized in the presence of the low acidic polymer component or vice versa. The pH of the composition is established at the desired level by the addition of ammonium hydroxide or sodium hydroxide. The composition can be used as a pressure sensitive adhesive, adhesive for lamination, textile adhesive, mosaic and packaging, or as a rubber band.

US-A-5, 314, 943 discloses a fast-curing, low-viscosity non-formaldehyde binder composition for textile materials. The composition consists of a latex, which is a copolymer based on a vinylaromatic compound and a conjugated diene, and a soluble copolymer which is obtained by copolymerizing a mixture of at least one ethylenically unsaturated polycarboxylic acid and at least one olefinically unsaturated monocarboxylic acid . The pH of the composition is set from 5 to 9 by means of ammonium hydroxide or sodium hydroxide. The composition is used as a binder for textile substrates. US-A-4, 868, 016 discloses a composition based on at least one thermoplastic latex polymer that is insoluble in an aqueous alkaline medium and at least one alkali-soluble polymer that is incompatible with the latex polymer. The latex polymer is a polymer dispersed in water which may be composed of acrylic or methacrylic esters, vinylaromatic compounds and vinyl esters and from 0.5 to 3% by weight of an ethylenically unsaturated carboxylic acid as an additional copolymer. The alkali-soluble polymer is also composed of these monomers, but contains from 10 to 60% by weight of an ethylenically unsaturated carboxylic acid. To set the pH to > 7, the composition may include ammonia, triethylamine, ethylamine or dimethylhydroxyethylamine. This can be used to provide substrates with a coating. It is known that stable aqueous (meth) acrylate dispersions formed by emulsion polymerization in the presence of protective colloids can be obtained only if at least 50% of the vinyl acetate, based on the total monomers, is incorporated by copolymerization. If the amount of vinyl acetate is less than 50% agglomeration occurs. US 4,670,505 describes as a solution to this problem a polyacrylate dispersion which is prepared by emulsion polymerization in the presence of from 0.1 to 5% by weight of at least one water-soluble amino alcohol having from 2 to 36 carbon atoms and from 0.4 to 5% by weight of a protective colloid, based in each case on the total monomers. The resulting latexes are of low viscosity and better pigment binding capacity, and are practically free of gel particles and stable to shear. An object of the present invention is to provide articles formed with formaldehyde-free binders that allow rapid curing at a low temperature and impart water resistance to the substrate. We have found that this objective is achieved by thermosetting compositions containing at least one polymer (Al), containing from 0 to 5% by weight of a mono- or dicarboxylic acid, β-ethylenically unsaturated acid in the form copolymerized and obtained by free radical polymerization in the presence of: a) at least one polymer (A2) obtainable by free radical polymerization and containing from 15 to 100% by weight of a mono- or dicarboxylic acid a, b- ethylenically unsaturated in copolymerized form, and b) at least one amine containing at least one long chain with at least 6 carbons, the weight ratio (based on solids) of the polymer (Al) to the polymer (A2) being from 7: 1 to 1: 7 and that of the polymer (A2) to the long chain amine being from : 1 to 2: 1. For the purposes of the present invention, the alkyl is preferably straight or branched chain C _ - C_. 8 alkyl, especially C 1 -C 12 alkyl, and, with particular preference, C 1 -C 4 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-dodecyl or n-stearyl. The hydroxyalkyl is preferably hydroxyalkyl Ci-Ce and, in particular 2-hydroxyethyl and 2- or 3-hydroxypropyl. The cycloalkyl is preferably C5-C7 cycloalkyl, especially cyclopentyl and cyclohexyl. The aryl is preferably phenyl or naphthyl.

Polymer (Al): Al polymer can be prepared using all monomers that can be polymerized by free radical polymerization. In general, the polymer Al is composed of: From 60 to 100 parts by weight, based on the total weight of the monomers for the Al polymer, of at least one copolymerizable monomer (main monomer), From 0 to 35 parts by weight , preferably from 0 to 20 parts by weight of at least one functional monomer (comonomer) and from 0 to 5 parts by weight, preferably from 0 to 3 parts by weight, of a α, β-unsaturated mono- or dicarboxylic acid, preferably from 0 to 3% by weight. The main monomer is preferably selected from: esters of α, β-monoethylenically unsaturated mono- or dicarboxylic acids, preferably C -Ce, such as acrylic, methacrylic, maleic, fumaric and itaconic acids, with alkanols in general of C _.- C? , preferably Ci-Cs and especially C1-C4. the particular esters are methyl, ethyl, n-butyl, isobutyl, tert-butyl and 2-ethylhexyl acrylate and methacrylate; - vinylaromatic compounds such as styrene, -methylstyrene, o-chlorostyrene or vinyltoluenes; vinyl esters of mono- or dicarboxylic acids of Ci-Ci8, such as acetate, propionate, n-butyrate, laurate and vinyl stearate; - Butadiene. Particularly preferred monomers are methyl methacrylate, methyl acrylate, n-butyl methacrylate, t-butyl methacrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, styrene and vinyl acetate. Suitable comonomers are in particular: linear 1-olefins, branched-chain 1-olefins or cyclic olefins, such as ethene, propene, butene, isobutene, pentene, cyclopentene, cyclahexene, octene, 2, 4, 4-trimethyl-1 -pentene alone or in mixture with 2,4,4-trimethyl-2-pentene, Cs-Cι olefin, 1-dodecene, C-olefin? -Ci4, octadecene, 1-eicosene (C2o) / C2o olefin ~ C24; oligoolefins prepared by metallocene catalysis and with a terminal double bond, such as oligopropene, oligohexene and oligooctadecene; olefins prepared by cationic polymerization and having a high α-olefin content, such as polyisobutene. However, preferably no ethene or linear 1-olefin is copolymerized in the polymer. - acrylonitrile, methacrylonitrile. vinyl and allyl C1-C40 alkyl ethers where alkyl can also carry substituents such as a hydroxyl, an amino or dialkylamino or one or more alkoxylate groups, examples being methyl, ethyl, propyl, isobutyl, 2-ethylhexyl, cyclohexyl, 4-hydroxybutyl, decyl, dodecyl, octadecyl, 2- (diethylamino) ethyl, 2- (di-n-butylamino) ethyl and methyldiglycol vinyl ether and the corresponding allyl ethers and / or mixtures thereofalkyl acrylamides and acrylamides such as acrylamide, methacrylamide, n-tert-butylacrylamide, n-methyl (meth) acrylamide. sulfo-containing monomers, such as allylsulfonic acid, methallylsulfonic acid, styrene sulfonate, vinylsulfonic acid, allyloxybenzenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, their corresponding alkali metal salts or ammonium salts, and mixtures thereof , and also sulfopropyl acrylate and sulfopropion methacrylate. C4-C4 hydroxyalkyl esters of C3-Ce mono- or dicarboxylic acids (see above), especially those of acrylic, methacrylic or maleic acid or their alkoxylated derivatives with from 2 to 50 mol of ethylene oxide, propylene, butylene oxide or mixtures thereof, or esters of C1-C1.8 alcohols, alkoxylated with from 2 to 50 moles of ethylene oxide, of propylene, butylene oxide or mixtures thereof, with the aforementioned acids, examples being (meth) hydrostylethyl acrylate, hydroxypropyl (meth) acrylate, 1,4-butanediol monoacrylate, ethyldiglyc acrylate, methyl polyglycol acrylate ( 11 EO), esters (meth) acrylic oxo alcohols of C? 3 / C_.5 that have reacted with 3, 5, 7, 10 or 30 moles of ethylene oxide, and mixtures thereof, vinylphosphonic acid, vinylphosphonate dimethyl and other monomers containing phosphorus. (metha) acrylates of alkylaminoalkyl or alkylaminoalkyl (meth) acrylamides or quaternization products thereof, examples being (meth) acrylate 2- (N, N-dimethylamino) ethyl, 3- (N, N-dimethylamino) propyl (meth) acrylate, chloride (meth) acrylate 2- (N, N, N-trimethylammonium) ethyl, 2-dimethylaminoethyl (meth) acrylamide, 3-dimethylaminopropyl (meth) acrylamide, 3-trimethylammonium propyl (meth) acrylamide chloride. alyl esters of C-C3o monocarboxylic acids - N-vinyl compounds such as N-vinylformamide, N-vinyl-N-methylformamide, N-vinylpyrrolidone, N-vinylimidazole, l-vinyl-2-methylimidazole, l-vinyl -2- methylimidazoline, N-vinylcaprolactam, vinylcarbazole, 2-vinylpyridine, 4-vinylpyridine. - diallyl ethylammonium chloride, vinylidene chloride, vinyl chloride, acrolein, methacrolein. monomers containing 1,3-diketo, as may be (meth) acrylate acetoacetoxyethyl or diacetone acrylamide, monomers containing urea groups, such as ureidoethyl (meth) acrylate, glycolic acrylamide acid, methacrylamido glycolate methyl ether. monomers containing silyl, such as trimethoxysilylpropyl methacrylate. monomers containing glycidyl, such as glycidyl methacrylate. Particularly preferred comonomers are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and hydroxyethyl methacrylate. Particular preference is given to hydroxyethyl acrylate and hydroxyethyl methacrylate, especially in amounts from 2 to 20% by weight, based on the total monomers Al.

The α, β-ethylenically unsaturated mono- and dicarboxylic acids are in particular those having from 3 to 6 carbons. Examples are acrylic, methacrylic, crotonic, fumaric, maleic, 2-methyl-maleate or itaconic acid and also the monoesters of the ethylenically unsaturated dicarboxylic acids, such as monoalkyl esters of maleic acid of C-C8 alkanols. The polymers can be prepared by customary polymerization techniques. For all methods of The customary apparatus is used for polymerization, the examples being stirred vessels, cascades of stirred vessels, autoclaves, tubular reactors and compounders. The polymerization is preferably carried out in the presence of compounds that form free radicals (initiators). The necessary amount of these compounds is preferably from 0.5 to 10, more preferably from 0.2 to 5% by weight, based on the monomers used in the polymerization. Examples of suitable polymerization initiators are peroxides, hydroperoxides, peroxodisulfates, percarbonates, peroxo esters, acid peroxides, and azo compounds. Examples of the initiators, which may be soluble or insoluble in water, are hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxodicarbonate, dilauroyl peroxide, methyl ethyl ketone peroxide, di-tert-butyl peroxide, acetyl acetone peroxide. , tert-butyl hydroperoxide, eumenal hydroperoxide, tert-butyl perneodecanoate, ter-amyl perpivalate, tert-butyl perpivalate, tert-butyl perneohexanoate, tert-butyl per-2-ethylhexanoate, tert-butyl perbenzoate , lithium, sodium, potassium and ammonium peroxodisulfates, azodiisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2- (carbamoylazo) isobutyronitrile and 4, -azobis (4-cyanovaleric acid). Other initiators of the The polymerization that can be used are the known redox initiator systems, such as H202 / ascorbic acid or t-butyl hydroperoxide / sodium hydroxymetansulfinate. The initiators can be used alone or in a mixture with each other, such as mixtures of hydrogen peroxide and sodium peroxodisulfate. For the polymerization in an aqueous medium, the use of water-soluble initiators is preferred. To prepare polymers of low average molecular weight it is often convenient to perform the copolymerization in the presence of regulators. Customary regulators can be used for this purpose, such as, for example, compounds containing organic SH such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, tert-butyl mercaptan, n-octylmercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan. , hydroxylammonium salts, such as hydroxylammonium sulfate, formic acid,. sodium bisulfite or isopropanol. In general, the polymerization regulators are used in amounts from 0.05 to 5% by weight, based on the monomers. To prepare copolymers of higher molecular mass it is often convenient to operate in the presence of crosslinkers in the course of the polymerization. These crosslinkers are compounds that have two or more groups ethylenically unsaturated, such as diacrylates or methacrylates of saturated alcohols when at least dihydric, examples being ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, diacrylate 1,4-butanediol, 1,4-butanediol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methylpentanediol diacrylate and 3-pentanediol dimethacrylate. The acrylic and methacrylic esters of alcohols having more than two OH groups can also be used as crosslinkers, the examples being trimethylolpropane triacrylate and trimethylolpropane trimethacrylate. Another class of crosslinkers is one containing diacrylates or dimethacrylates of polyethylene glycols or polypropylene glycols having molecular weights of from 200 to 9000 in each case. In addition to the homopolymers of ethylene oxide and / or propylene oxide it is also possible to use copolymers in block of ethylene oxide and propylene oxide or copolymers of ethylene oxide and propylene oxide containing the units of ethylene oxide and propylene oxide in random distribution. The oligomers of ethylene oxide and / or propylene oxide are also suitable for the preparation of the crosslinkers, the examples being diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate and / or tetraethylene glycol dimethacrylate. Other suitable crosslinkers are vinyl acrylate, vinyl methacrylate, vinyl itaconate, divinyl adipate, butanediol divinyl ether, trimethylolpropane trivinyl ether, allyl acrylate, allyl methacrylate, pentaerythritol triallyl ether, triallyl sucrose, pentaallyl sucrose, methylenebis (met) acrylamide, divinylethylene urea, divinylpropylene urea, divinylbenzene, divinyl dioxane, triallyl cyanurate, tetraallylsilane, tetravinylsilane and bis- or polyacrylic siloxanes (for example, TegomerU) products of Th. Goldschmidt AG). Preferably, the crosslinkers are used in amounts of 10 ppm to 5% by weight, based on the monomers to be polymerized.

The polymer Al is usually prepared in water as a dispersion medium. However, organic solvents miscible in water, such as alcohols and ketones, examples being methanol, ethanol, n-propanol, isopropanol, n-butanol, acetone or methyl ethyl ketone, may also be present in a proportion of about 30% in volume. The result is a fine, stable polymer dispersion. The particle sizes can be determined by the customary methods for emulsion polymers watery For example, particle sizes determined by means of quasi-elastic light scattering are generally in the range of 30 to 1500 nm, preferably from 40 to 500 nm. The particle size distribution can be monomodal or polydaldal. The preparation of the Al polymer is preferably carried out only with the acid-rich polymer A2 and the long-chain amine as the only stabilizing agents of the resulting dispersion particles. The polymer A2 and the long chain amine form a polymeric ammonium salt which stabilizes the resulting polymer particles or polymer droplets and thereby gives rise to stable polymer dispersions with a low coagulum content. Without the acid-rich polymer A2 the resulting polymer dispersions lack water resistance and have poor thermal stability. The omission of the long-chain amine causes in many cases coagulation of the polymerization mixtures. In addition to the stabilization by the polymer A2 and the long chain amine, however, it is also possible, during the preparation of Al, to add surface active auxiliaries, such as emulsifiers or protective colloids. Of the emulsifiers or protective colloids commonly used for this purpose, anionic, nonionic, cationic and amphoteric emulsifiers are suitable. Preference is given to anionic emulsifiers, such as alkylbenzene sulfonic acids, sulfonated fatty acids, sulfosuccinates, fatty alcohol sulfates, alkyl phenol sulfates and fatty alcohol ether sulphates. Examples of the nonionic emulsifiers which may be used are alkylphenol ethoxylates, primary alcohol ethoxylates, fatty acid ethoxylates, alkanolamide ethoxylates, EO / PO block copolymers and alkyl polyglucosides. Examples of the cationic and / or amphoteric emulsifiers used are quaternized amino-alkoxylates, alkylbetaines, alkylamidobetaines and sulfobetaines. Examples of the common protective colloids are cellulose derivatives, polyethylene glycol, polypropylene glycol, ethylene glycol and propylene glycol copolymers, polyvinyl acetate, polyvinyl alcohol, polyvinyl ether, starch and starch derivatives, dextran, polyvinylpyrrolidone, polyvinylpyridine, polyethylene imine, polyvinylimidazole, polyvinyl succinimide, polyvinyl-2-methylsuccinimide, polyvinyl-1,3-oxazolid-2-one and polyvinyl-2-methylimidazoline. Emulsifiers or protective colloids usually they are used in concentrations of less than 5% by weight, based on the monomers. It is preferred to work without emulsifiers or protective colloids. The monomers may be neutralized in whole or in part, before or during the polymerization, by means of customary inorganic or organic bases. Examples of suitable bases are alkali metal or alkaline earth metal compounds, such as sodium, potassium or calcium hydroxide, sodium carbonate, ammonia and primary, secondary or tertiary amines, such as di- or triethanolamine. It is particularly preferred to carry out the neutralization before or during the polymerization. Even after the polymerization, it is preferred not to add any neutralizing agent, in addition to the alkanolamine that can be added. The polymerization is carried out continuously or discontinuously in the customary manner and according to a large number of variants. When the polymerization process described above is used in the presence of a. polymer (A2) and the long chain amine, polymers (Al) with a weight average molecular weight of from 1,000 to 5,000,000, preferably from 5,000 to 2,000,000, are obtained. An accessible measure for the average molecular weight of a polymer is its value K. The K value is a number of relative viscosity that is determined in analogy with DIN 53726. This consists of the flow velocity of the. pure solvent in relation to the flow rate of a solution of polymer A2 in this solvent. A high value for K corresponds to a high average molecular weight (see, Cellulosechemie, vol. 13, (1932), pp. 58-64 and Kirk-Othmer, Encyclopedia of Chemical Technology, vol. 23, pp. 967-968). The K values are generally in the range from 15 to 150 (1% concentration by weight in dimethylformamide). The emulsion polymerization can be carried out so that the solids content is in the range of 20 to 70%, preferably from 30 to 60% by volume. From 15 to 100% by weight of polymer (A2), preferably from 20 to 100% by weight, in particular from 40 to 100% by weight, and particularly preferably from 60 to 100% by weight is composed of at least one α, β-ethylenically unsaturated mono- or dicarboxylic acid. The polymer may also be present partly or completely in the form of a salt; the acid form is preferred. The solubility in water of the polymer in the acid form of preference is > 10 g / 1 (at 25 ° C). The weight average molecular weight of the polymer (A2) is greater than 500 and generally less than 5 million. The K values of the polymers (according to H. Fikentscher, Cellulose-Chemie 13 (1932), pp. 58-64, 71 and 74), which are a measure of molecular weight, are in general in the range from 10 to 150 (measured in an aqueous solution at 1% concentration by weight). The polymer generally has at least 4 carboxylic acid groups, or salt groups derived therefrom, per polymer chain. The ethylenically unsaturated carboxylic acids which can be used have already been specified above in relation to the polymer (Al). Particular preference is given to polymers including maleic acid, such as copolymers of maleic and acrylic acids. It is also possible to obtain the polymers starting from ethylenically unsaturated mono- or dicarboxylic anhydrides alone or in a mixture with the aforementioned carboxylic acids. Under the conditions of the polymerization, for example in the solution or emulsion polymerization in an aqueous medium, or after the polymerization, the anhydride functions are converted to carboxylic acid groups by the reaction with a base or acid. The ethylenically unsaturated carboxylic anhydrides which can be used are, in particular, maleic, itaconic, acrylic and methacrylic anhydrides. In addition to the mono- or dicarboxylic acids, the polymer (A2) can also include, in copolymerized form, from 0 to 8151% by weight, preferably from 0 to 80% by weight, in particular from 0 to 60% by weight with particular preference from 0 to 40% by weight of at least one other monomer. The monomers that can be used have already been specified above in relation to the polymer (Ai). Preference is given to methyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, methyl acrylate, ethyl acrylate, n-Butyl acrylate, 2-ethylhexyl acrylate, styrene, acrylamide, acrylonitrile and vinyl acetate. The polymerization process and auxiliaries have already been described above in relation to the polymer (Al). In addition to the polymerization techniques specified above in relation to the polymer (Al), the polymers (A2) can also be obtained by a solution polymerization. The use of polymerization in aqueous solution by free radicals yields the water-soluble polymers and the A2 copolymers, preferably starting from 50 to 100% by weight of the aforementioned carboxylic acids, carboxylic anhydrides, monoesters or a mixture of two or more of these compounds. Its weight average molecular weight is generally in the range from 500 to 1,000,000, preferably from 200 to 200,000. The K values of the polymers are generally in the range from 10 to 150, preferably from 12 to 100 (measured in a solution in water at 1% concentration by weight). The content of solids it is generally in the range from 10 to 80% by weight, preferably from 20 to 65% by weight. The polymerization can be carried out from 20 to 300 ° C, preferably from 60 to 200 ° C. The solution polymerization is carried out in a customary manner, as described, for example, in EP-A-75 820 or DE-A-36 20 149. The polymer (A2) can also be obtained by grafting maleic acid or maleic anhydride, or a monomeric mixture containing maleic acid or maleic anhydride, on a grafted base. Examples of suitable grafted bases are monosaccharides, oligosaccharides, modified polysaccharides and alkyl polyglycol ethers. Examples of these grafted polymers are described in DE-A-4 003 172 and EP-A-116 930. The polymer A2 can also be prepared in a two-stage process directly before the preparation of the Al polymer in the same reaction vessel . The long chain amine is preferably an amine of the formula: RxNRyRz where Rx is C6-C22 alkyl, C6-C22 alkenyl, Cg-C22 arylalkyl or Cd-C2 arylalkenyl and the alkenyl can have from 1 to 3 double bonds, R? and Rz, which can be equal or different, are H, (-CH2-CH20-) nH, where n is 1 to 25, or C5-C7 cycloalkyl which is unsubstituted or substituted by at least one hydroxyl, or they are as defined for Rx or together they are a ring of 5 to 7 members which may contain at least other heteroatoms selected from O, N and S. Preferred Rx radicals are those having from 8 to 22 carbons. The long chain amine is in particular selected from compounds of the above formula in which R is C6-C22 alkyl or Ce-C22 alkenyl (preferably having 1 to 2 double bonds) and Ry and Rz, which are the same or different, are H or (CH2CH2?) nH. Preferably, it is from 1 to 20, especially from 1 to 10. Examples of suitable long chain amines are those ethoxylated amines marketed by AKZO under the name "Ethomeen" such as Ethomeen C / 15, a polyoxyethylene- (5) -cocoamine, or Ethomeen S / 12, an oleylbis (2-hydroxyethyl) amine, or Ethomeen T / 25, a polyoxyethylene- (15) -seboamine. Products of this class are also available to other suppliers. Other examples that may be mentioned at this point are Lutensol FA 12 from BASF, a polyoxyethylene- (12) -oleilamine, or Noramox 0.7 from Pierrefitte-Auby, a polyoxyethylene- (7) -olethylamine. Long-chain, ethoxylated mono- or diamines are preferred. For the preparation of the compositions However, it is also possible to use long chain, primary, secondary or tertiary aliphatic amines. Examples of these are the products of AKZQ Armeen DMOD (oleildi ethylamine), Armeen M2C (dicocomethylamine), Armeen NCMD (N-cocomorfoline), Armeen 2C (dicocoamine) or Armeen 12D (n-dodecylamine). The composition can, if desired, also include at least one alkanolamine having at least two hydroxyls. The addition of the alkanolamine gives rise to a faster curing of the novel compositions at a certain curing temperature, or curing at a lower temperature with a predetermined curing time. In addition, the addition of an alkanolamine improves the film-forming ability of a composition. Suitable alkanolamines are those of the formula: where R is H, C1-C5 alkoyl or hydroxyalkyl of C _.C_.o, and b c R and R are hydroxyalkyl of C_.C.o. With particular preference, Rb and Rc independently are a C2-C5 hydroxyalkyl and Ra is H, C1-C5 alkyl or C2-C5 hydroxyalkyl. Examples of the alkanolamines are diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, methyldiethanolamine, butyldiethanolamine and methyldiisopropanolamine. Triethanolamine is particularly preferred. Also suitable are the alkanolamines selected from linear or branched, water-soluble aliphatic compounds which contain per molecule at least two amino functional groups of the type (a) or (b) (a) (b) where R is hydroxyalkyl and R 'is alkyl. These compounds preferably contain at least one compound of the formula I: where A is C2-C18 alkylene which is unsubstituted or substituted by one or more groups independently selected from 6 * 7 alkyl, hydroxyalkyl, cycloalkyl, OH and NR R, where R and R are independently H, hydroxyalkyl or alkyl, and interrupted or interrupted by one or more oxygens and / or NR groups, where R is H, hydroxyalkyl, (CH2) nNR6R7 / where n is 2 to 5 and R6 and R7 they are as defined, or alkyl, which in turn is interrupted by one or more groups NR5, where R5 is as defined above and / or is substituted by one or more groups NR R, where R and R are as defined; or A is a radical of the formula: where o, q and y independently are 0 or an integer from 1 to 6, pyr independently are 1 or 2, and t is 0, 1 or 2, where the cycloaliphatic radicals can also be substituted by 1, 2 or 3 alkyls, and R 1 , R2 and R3 and R4 independently are H, hydroxyalkyl, alkyl or cycloalkyl, the compounds having at least two or preferably at least three hydroxyalkyls per molecule. Particular preference is given to: (1) compounds of the formula where i is C2-C2 alkylene which is unsubstituted or substituted by at least one alkyl and / or when 6 7 minus one group NR R where R and R independently are alkyl or hydroxyalkyl, and R 1, R 2, R 3 and R 4 independently are hydroxyalkyl or H, or one of R and R and / or one of R and R is alkyl or cycloalkyl. Particularly useful compounds of this type are those of the following formulas: where x is 2 to 12, especially 2, 3, 6, 8, 10 or 12, The compounds of the formula also include the aminals of the formula [2) The compounds of the formula Ib wherein A2 is C2-C8 alkylene which is interrupted by at least one NR group, where R (or each R independently) is hydroxyalkyl or alkyl, and R 1, R 2, R 3 and R 4 i. Are independently hydroxyalkyl or H. The radical A2 is preferably interrupted by one or two NR groups. The particularly useful compounds of this type are those of the following formulas [3] The compounds of the formula le: where A3 is C2-C8 alkylene which is interrupted by at least one NR group, where R is H,. hydroxyalkyl or CH2CH2NR6R7, 1 2 3 4 R, R, R and R independently are alkyl which is uninterrupted or interrupted by at least one group NR and / or unsubstituted or substituted by when less a group NR 6"R7, R ~ is H, hydroxyalkyl or -R NR 6 ^ R7, and fi R and R independently are H, hydroxyalkyl or -R8NR6R7, R is an ethylene or propylene radical, and where (on average ) at least 30%, in particular > 60% and preferably > 80% of the nitrogens (hydroxyalkyl) carry a hydroxyalkyl. The C2-Cs alkenylene group is preferably interrupted by at least two NR groups. Particularly useful compounds of this type are reaction products and ethylene oxide with polyethyleneimines of different molecular weights, containing two or more structural units NR R and NR. The polyethylene imines that can be used are those whose weighted average molecular weight is in the range from 400 to 2,000,000. The formula in the following diagram is proposed to illustrate compounds of this type: where R is H, hydroxyethyl or -R8NR6R7 and R6 and R7 are H, hydroxyethyl or -R8NR6R7 and R8 is (CH2) 2 / in which on average > 40%, especially > 60% and with particular preference > 80% of the ethoxylatable NH functions of polyethyleneimine have reacted with ethylene oxide. (4; Compounds of the formula le where 5 is C 6 -C 8 alkylene which is interrupted by at least one NR group, where R is (CH 2) n NR R or alkyl that is uninterrupted or interrupted by at least one group NR, cf 1 'where R is ( CH2) nR or alkyl and / or is unsubstituted or substituted by at least one group NR6R7, n is 2 or 3, and 2 3 R1, R, R R4, R and R independently are hydroxyalkyl or H. Particularly useful compounds of this type are polyamines of the formulas: OH (5) The compounds of the formula If where ? is alkylene of C -C_.2 which is interrupted by at least one oxygen, and 1 2 3 4 R, R, R and R independently are hydroxyalkyl or H. The alkylene chain is preferably interrupted by 1, 2 or 3 oxygens. Particularly useful compounds of this type are the compounds of the following formulas: 6) The compounds of the formula Ig, where o, q and s independently are 0 or an integer from 1 to 6; pyr independently are 1 or 2, and t is 0, 1 or 2, it being possible for the cycloaliphatic rings to be substituted by 1, 2 or 3 alkyls, and R 1, R 2, R 3, R 4 independently are hydroxyalkyl or H. Particularly useful compounds of this type are: (7) Polyalkanolamines which are obtained by condensation of di- or trialkanolamines with one another or with themselves, alone or in the presence of alcohols or amines with a functionality of one or more.

An example of these oligomeric or polymeric compounds is the condensation product prepared from triethanol which is represented in an idealized form by the following formula in diagram: R » The compounds of the formula la, Ib (with the exception of the aforementioned aminals), Le, Id, Le, If and Ig can be prepared by reacting the corresponding polyamines with alginylene oxides. The reaction of amines with alkylene oxides, especially ethylene oxide and propylene oxide, to the corresponding alkanolamines is known in principle. For this purpose, the amines react in the presence of a proton donor, generally water, with the alkylene oxides, generally from 30 to 120 ° C, under atmospheric or superatmospheric pressure, preferably from 1 to 5 bar, using approximately one equivalent of the alkylene oxide by NH function to be alkoxylated. For the almost complete alkoxylation it is possible to use a small excess of alkylene oxide, although the use is preferred of the stoichiometric amount or even a slight deficit of alkylene oxide relative to the N-H functions. The alkoxylation can be carried out with an alkylene oxide or with a mixture of two or more alkylene oxides. Otherwise, the alkoxylation can be carried out with two or more alkylene oxides in succession. Suitable catalysts besides water are alcohols or acids, although water is preferred (with respect to the alkoxylation of the amines see, N. Schonfeld, Grenzfláchenaktive Ethylenoxid-Addukte [ethylene oxide addition products, surface active agents], pp. 29-33, issenschaftliche Verlagsgesellschaft mbH, Stuttgart 1976 or SP McManus et al., Synth, Comm. 3, (1973) 177). The amount of water used as catalyst and / or solvent may vary depending on the requirements. In the case of liquid amines of low viscosity, amounts of water from 1 to 5% are sufficient to catalyze the reaction. Solid, highly viscous or polymeric amines react favorably as solutions or dispersions in water; in this case the amount of water can be from 10 to 90%. Under the conditions described for the alkoxylation in the presence of water, virtually only the -NH groups react. The alkoxylation of the resulting OH groups, in general, is not carried out, so that it is carried out practically a monoalkoxylation of the NH groups (in other words, no more than one mole of alkylene oxide is added per mole of NH). The average degree of alkoxylation of the active NH groups is preferably > 75% in the case of compounds that have less than 5 nitrogens per molecule. Examples of the starting polyamines which can be used are α, β-oligomethylenediamines, such as 1,2-ethylenediamine, 1,3-propanediamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,12-dodecamethylenediamine, 2,2-dimethyl-1,3-propanediamine, 1,2-propanediamine, 2- (ethylamino) ethylamine, 2- (methylamino) propylamine, N- (2-aminoethyl) -1,2-ethanediamine, N- (2 -aminoethyl) -1,3-propanediamine, N- (2-aminoethyl) -N-methylpropanediamine, N, N-bis- (3-aminopropyl) ethylenediamine, 4-aminoethyl-l, 8-octanediamine, 2-butyl-2 ethyl-l, 5-pentadiamine, 2,2,4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, 1,3-diaminopentane, 3-isopropylaminopropylamine, triethylenetetramine or tetraethylenepentamine. The oligo- and poly-N- (β-hydroxyethyl) amino compounds (aminals) can also be prepared by condensation of aliphatic dialdehydes and diethanolamine. The poly-N- (β-hydroxyethyl) amino compounds (8) are obtained as described, for example, in US-A-4, 505, 839 and in DE-A-3 206 459 by thermal condensation of triethanolamine to obtain poly (triethanolamine) or by thermal condensation of alkanolamines to obtain hydroxyl-containing polyethers. The condensation of the alkanolamines can also be carried out, as described in DE-A-1 243 874, in the presence of primary or secondary amines or alcohols with a functionality of 1 or more. Depending on the conditions of the condensation, the molecular weight of these products and thus the viscosity, can vary within a wide range. The weighted average molecular weights of these polycondensates are usually from 200 to 100,000. The compounds of the formulas can be prepared by alkoxylation of what are known as dendrimer polyamines, the synthesis of which by the Michael addition of aliphatic diamines in acrylonitrile and the subsequent catalytic hydrogenation is described in WO 93/14147. An example of these compounds is the hydrogenated addition product of 4 moles of acrylonitrile and ethylenediamine. This test having 4 primary amines can also react in a similar way to obtain the N-14 amine with 8 primary amines. Instead of ethylenediamine, it is also possible to use other di- and aliphatic polyamines. Amino-containing polymers, such as polyethyleneimine, can also react with ethylene oxide in aqueous solution to form useful poly-N- (β-hydroxyethyl) amino compounds, the degree of conversion being of the generally present NH functions > 40%, especially greater than 60% and preferably greater than 80%. The preparation of polyethyleneimine is a general knowledge. The polyethyleneimines in the molecular weight range Mw = 800 to 2,000,000, for example, are obtained from BASF under the name Lupasol®. Polyethylene imines generally consist of branched polymer chains and, therefore, contain primary, secondary and tertiary amines. Its ratio is usually about 1: 2: 1. At very low molecular weights, however, higher ratios of primary amines are also possible. Also suitable for this application are the substantially linear polyethyleneimines which are obtained by special preparation techniques. Polymeric alkyleneimines having primary and / or secondary amines, which after alkoxylation can be used in novel compositions, are described in the "Encyclopedia of Polymer Science and Engineering", H. Mark (ed.), Revised Edition, Vol. 1, pp. 680-739, John Wiley &Sons Inc., New York, 1985. It is also possible to prepare polyalkyleneimines substituted with hydroxyalkyl by polymerization of N-hydroxyalkylaziridines Alkoxylated allylamine polymers and copolymers can also be used in the compositions Novelty The compounds of the formula If can be prepared starting from oxamines, such as 4,7-dioxadecan-1, 10-diamine, 4,9-dioxadecan-1, 12-diamine, 4,11-dioxatetradecan-1, 14-diamine, 4, 9-dioxadodecan-1, 12-diamine and 4, 7, 10-trioxatridecan-1, 13-diamine. Other suitable initial amines are polyoxyalkyleneamines, which are marketed by Huntsman under the name Jeffamine®. Examples of these are diaphragms Jeffamine D-230, Jeffamine-D-400, Jeffamine D-2000, Jeffamine D-4000, Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED-2001 and Jeffamine EDR-148 and triamines Jeffamine T-403, Jeffamine T-3000 and Jeffamine T-5000. The reaction products of aromatic polyamines with alkylene oxide are also suitable in principle for use in novel compositions. The polymers (Al) and (A2) are preferably used in a weight ratio from 5: 1 to 1: 5 and with particular preference from 3: 1 to 1: 3 (based on the non-volatile fractions). The weight ratio of the polymer (A2) to the long chain amine is from 20: 1 to 2: 1 (based on the non-volatile fractions), preferably from 10: 1 to 3: 1. The weight ratio of the polymer (A2) to the alkanolamine (if present) is preferably from 100: 1 to 1: 1, especially from 50: 1 to 2: 1 and, preferably particular, from 30: 1 to 2.5: 1 (based in each case on the non-volatile fractions). Particularly preferred proportions are as follows: 40-60 parts by weight of polymer (Al) 20-40 parts by weight of polymer (A2) 6-10 parts by weight of long chain amine, and if 0-15 parts are used by weight of alkanolamine Preferably, the alkanolamine is added to the novel composition after preparation. This can be added in undiluted form or as an aqueous solution. An alternative possibility is to prepare the novel composition in the presence of an alkanolamine. The pH of the novel compositions is from 0 to 9, preferably from 0.5 to 6, with particular preference from 1 to 4. A low pH promotes the heat cure of the compositions. At a content of active ingredients of 40% by weight, the viscosity of the novel aqueous compositions is generally in the range from 10 to 10,000 mPa.s, measured in a rotary viscometer according to DIN 53019 at 23 ° C, and at a speed cutting of 250 s. Preference is given to viscosities from 20 to 20,000 mPa.s, especially from 30 to 5,000 mPa.s.

The novel compositions have a non-volatile content in the range from 20 to 75% by weight, preferably from 40 to 70% by weight. The novel compositions may include a reaction accelerator, but preferably do not include it. Examples of suitable reaction accelerators are hypophosphites, phosphites, polyphosphates and diacid alkali metal phosphates, polyphosphoric acid, hypophosphoric acid, phosphoric acid, alkylphosphinic acid or oligomers or polymers of these salts and acids. Other suitable catalysts are strong acids such as sulfuric acid and p-toluenesulfonic acids. Also suitable are polymeric sulfonic acids, such as poly (acrylamido-2-methylpropanesulfonic acid), polyvinylsulfonic acid, poly (p-styrenesulfonic acid), poly (sulfopropyl methacrylate) and polymeric phosphonic acids such as poly (vinylphosphonic acid). ), for example, and also copolymers derived therefrom with the comonomers described above. It is also possible to incorporate sulfonic acids or phosphonic acids that induce acceleration in the acid-containing polymer (A2) using the corresponding monomers, such as acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, p-styrenesulfonic acid, sulfopropyl methacrylate or acid vinylphosphonic, as comonomers when polymeric carboxylic acids are prepared. Other suitable catalysts are organotitanatos and organocirconates, such as triethanol titanate, titanium chelate ETAM and tetrabutylcirconate, which are marketed, for example, by Hüls. In addition, novel compositions may, depending on their intended use, contain customary additives, such as bactericides or fungicides, for example. In addition, these may contain hydrophobing agents to increase the water resistance of the treated substrates. Suitable hydrophobing agents are customary aqueous paraffinic dispersions or silicones. The compositions may also include wetting agents, thickeners, plasticizers, retention agents, pigments and fillers. Finally, the novel compositions may contain agents customary for providing fire protection, such as aluminum silicates, aluminum hydroxides, borates and / or phosphates. In many cases, the compositions also contain coupling reagents, such as alkoxysilanes, an example being 3-aminopropyltriethoxysilane, soluble or emulsifiable oils as lubricants and powdered binders, and also wetting aids.

The novel compositions can also be used in a mixture of other binders such as, for example, urea-, melamine- or phenyl-formaldehyde resins, and with epoxy resins. The novel compositions are free of formaldehyde. Formaldehyde-free means that the novel compositions do not contain substantial amounts of formaldehyde and also that in the drying and / or curing no substantial amounts of formaldehyde are released. In general, the formaldehyde content of the compositions is < 100 ppm. The compositions make possible the preparation of shaped articles that require a short curing time, and produce shaped articles with excellent mechanical properties. The novel thermosetting compositions, without formaldehyde, are virtually non-crosslinked during use and therefore are thermoplastic. However, if necessary, it is possible to establish a small degree of pre-crosslinking using, for example, monomers having two or more polymerizable groups. With heating the water in the composition evaporates and the composition is cured. These processes can be carried out in succession or simultaneously. Curing is understood in this context as the chemical modification of the composition; for example, crosslinking by formation of covalent bonds between the different constituents of the compositions, the formation of ionic interactions and groupings, the formation of hydrogen bonds. Curing may also include physical changes in the binder, such as phase transformations or phase inversion. Curing is carried out from 75 to 250 ° C, preferably from 90 to 200 ° C and, with particular preference, from 100 to 180 ° C. The duration and level of heating influences the degree of curing. An advantage of the novel compositions is that they can be cured at comparatively low temperatures. The curing can be carried out in two or more stages. For example, in a first stage the temperature and time of curing can be chosen so that only a low degree of curing is obtained, and the practically complete curing is carried out in a second stage. This second step can be carried out in spatial and temporal separation of the first step. This allows the novel compositions to be used, for example, to produce semi-finished products, impregnated with binder, which can be formed and cured to term at a different site. The compositions are used in particular as binders for the production of shaped articles, made from fibers, flakes or pieces, which can be renewable raw materials or synthetic or natural fibers, for example from garment waste. As renewable raw materials, mention may be made in particular of henequen, jute, flax, coconut fibers, hemp variety, banana fibers, hemp and cork. Wood fibers and wood chips are particularly preferred. The articles preferably formed have a density from 0.2 to 1.4 g / cm3 at 23 ° C. Suitable shaped articles are, in particular, sheets and parts with irregular curves. Its thickness is generally at least 1 mm, preferably at least 2 mm, and its surface area is usually from 200 to 200,000 cm Particularly suitable articles are interior parts for automobiles, such as interior door shutters, instrument panels, dashboard drawers. The amount by weight of the binder used is generally from 0.5 to 40% by weight, preferably from 1 to 30% by weight (in terms of the binder solids) with base 'on the substrate (fibers, chips or chips). The fibers, chips or chips can be coated directly with the binder or mixed with the aqueous binder. The viscosity of the aqueous binder is preferably established (especially in the case of the production of articles formed from fibers of wood or wood shavings) from 10 a. 10,000, more preferably from 50 to 5000, and very particularly preferably from 100 to 2500 mPa-s (DIN 53019, rotating viscometer 250 s). The mixture of fibers, chips and chips and the binder can initially be dried from 10 to 150 ° C, for example, and then compressed at 50 to 250 ° C, preferably from 100 to 2-40 ° C and, with particular preference , from 120 to 225 ° C and at pressures generally from 2 to 1000 bar, preferably from 10 to 750 bar and, with particular preference, from 20 to 50 bar to obtain the articles formed. Binders are particularly suitable for producing wood-based materials such as ordinary wood boards and wood pulp cartons (see Ullmanns Encyclopaedia der technischen Chemie, 4th edition 1976, volume 12, pp. 709-727), which they can be produced by glueing disintegrated wood, such as wood shavings and wood fibers, for example. The water resistance of wood-based materials can be improved by adding a customary commercial paraffin aqueous dispersion or other hydrophobing agents to the binder, or adding the hydrophobing agents in advance or later to the fibers, flakes or chips. The production of cardboard is widely known and describes, for example, in HJ Deppe, K. Ernst, Taschenbuch der Spanplattentechnik, 2nd edition, Verlag Leinfelden 1982. It is preferred to use shavings whose average size is from 0.1 to 4 mm, in particular from 0.2 to 2 mm, and it contains less than 6% by weight of water. However, it is also possible to use considerably thicker chips with a higher moisture content. The binder is applied with great uniformity to the wood chips, the weight ratio of the binder solids / wood chips being preferably from 0.02: 1 to 0.3: 1. A uniform distribution can be obtained, for example, by spraying the binder in finely divided form on the chips. The glued wood chips are then dispersed to form a layer with a highly uniform surface, the thickness of the layer being guided by the desired thickness of the finished board. The dispersed layer is compressed from 100 to 250 ° C, preferably from 120 to 225 ° C, applying pressures usually from 10 to 750 bar, to form a board. The necessary compression times can vary within a wide range and are generally from 15 seconds to 30 minutes. The wood fibers of adequate quality required to produce panels of medium density fibreboard (MDF) of the binders can be prepared from wood chips without bark by grinding in special mills or refiners at approximately 180 ° C. For gluing, the wood fibers are generally subjected to a turbulent flow in an air stream and the binder is sprayed onto the generated fiber stream (process in "blow line"). The ratio of the wood fibers to the binder, based on the content of the dry matter or solids content, is usually from 40: 1 to 2: 1, preferably from 20: 1 to 4: 1. The glued fibers are dried in the fiber stream from 130 to 180 ° C, for example, spread to form a network of fibers and compressed at pressures from 10 to 50 bar to form sheets or articles formed: The wood fibers glued also they can be processed, as described in DE-A-2 417 243, for example, in a transportable fiber folder. This semi-finished product can then be processed in a second, temporary and spatially separate step to form sheets or formed articles, such as interior shutter panels in motor vehicle doors. Other natural fiber substances also, such as henequen, jute, hemp, flax, coconut fibers, banana fibers and other natural fibers, can be processed with the binders to form sheets and formed parts. Natural fiber materials can also be used in mixtures with plastic fibers such as polypropylene, polyethylene, polyesters, polyamides or polyacrylonitrile. In this case, the plastic fibers can also function as co-binders in addition to the novel binder. The proportion of the plastic fibers is preferably less than 50% by weight, in particular less than 30% by weight and, with particular preference, less than 10% by weight, based on all chips, flakes or fibers. The fibers can be processed by the methods used for the wooden boards. Otherwise, the preformed natural fiber binders can be impregnated with the novel binders, with or without the addition of a wetting aid. The impregnated folders are then compressed, in the state wetted with the binder or pre-drying, from 100 to 200 ° C and at pressures from 10 to 100 bar, for example to form sheets or formed parts. The substrates impregnated with the novel binders preferably have a residual moisture content, during compression, of 3-20% by weight, based on the substrate to be bound. The shaped articles obtained according to the invention have low water absorption, little increase in thickness (swelling) after storage in water and good strength and are free of formaldehyde. In addition, novel compositions can be used as binders for coating and impregnation compositions for organic and / or inorganic fiber sheets, non-fibrous mineral fillers and also aqueous starch and / or polymer dispersions. The coating and impregnating compositions give the sheets a high flexural modulus. The production of these leaves is known. The sheets of this kind are commonly used as panels for sound insulation. The thickness of the sheets is usually in the range from about 5 to 30 mm, preferably from 10 to 25 mm. The marginal length of square or rectangular sheets is usually in the range from 200 to 2000 mm. In addition, the novel compositions may contain auxiliaries accustomed to coating and impregnation technology. Examples of these auxiliaries are finely divided inert fillers, such as aluminum silicates, quartz, precipitated or pyrogenic silica, light and heavy spar, talc, dolomite or calcium carbonate; pigments that impart color, such as titanium white, zinc white, iron oxide black, etc., foam inhibitors, such as modified dimethylpolysiloxanes and adhesion promoters and preservatives. The components of the novel composition are present in the coating composition in general in an amount from 1 to 65% by weight. The proportion of inert fillers is generally from 0 to 85% by weight, while that of water is at least 10% by weight. The compositions are used in a customary manner by application to a substrate, for example by spraying, rolling, casting or impregnation. The amounts applied, based on the dry content of the composition, are in general from 2 to 100 g / m. The amounts of additives to be used are known to those skilled in the art and depend, in each individual case, on the desired properties and the proposed use. The novel compositions are also useful as binders for insulating materials made from inorganic fibers, such as mineral fibers and glass fibers. These insulating materials are produced in industrial form by melt spinning of the corresponding mineral raw materials: see US-A-2, 550, 465, US-A-2,604,427, US-A-2,830,648, EP-A-354 913 and EP -A-567 480. The composition is then sprayed on the freshly produced and still hot inorganic fibers. The water then evaporates substantially and the composition remains adhered, in a virtually uncured state, as a viscous mass on the fibers. A continuous folder, of fibers containing binder, produced in this way It is transported through a curing oven by means of suitable conveyor belts. There, the folder is cured from approximately 100 to 200 ° C to form a rigid matrix. After curing, the insulating folders are finished properly. The main proportion of the mineral or glass fibers used in the insulating materials has a diameter in the range of 0.5 to 20 μ and a length in the range of 0.5 to 10 cm. The novel compositions are also suitable as binders for continuous fiber materials. Examples of continuous fiber materials are continuous cellulose acetate, cellulose acetate, cellulose esters and ethers, cotton, hemp, animal fibers, such as wool or hair and especially non-woven fabrics of synthetic or inorganic fibers, for example aramid , carbon, polyacrylonitrile, polyester, mineral, PVC or glass fibers. When used as binders for continuous fiber materials, the novel compositions may, for example, include the following additives: silicates, silicones, boron-containing compounds, lubricants, wetting agents. Fiberglass continuous materials are preferred. Continuous materials of non-agglomerated fibers (continuous raw material fiber materials), especially those made of glass fiber, are bonded, that is, consolidated, by the novel binder. The novel binder is preferably applied to the continuous raw material fiber material, by coating, impregnation or soaking, for example, in a weight ratio of fiber / binder (solids) from 10: 1 to 1: 1, more preferably from 6: 1 to 3: 1. In this case, the use of the binder in the form of an aqueous, diluted formulation containing 95 to 40% by weight of water is preferred. The application of the binder to the continuous material of raw material fibers is generally followed by drying, preferably from 100 to 400 ° C, especially from 130 to 280 ° C, and with very particular preference, from 130 to 230 ° C, during a period of preference from 10 seconds to 10 minutes, in particular from 10 seconds to 3 minutes. The continuous material of agglomerated fibers obtained has a high resistance in the dry and wet states. In particular, the novel binders allow short drying times and also low drying temperatures. Continuous agglomerated fiber materials, especially glass fiber continuous materials, are suitable for use as or in roofing membranes, as base materials for wallpaper or as coatings or base material for coatings for finished floors, for example, PVC. In the case of use as roofing membranes, continuous agglomerated fiber materials are generally coated with bitumen. The aqueous compositions of this invention can also be used to produce foamed boards or articles formed. For this purpose, the water present in the composition is initially removed at temperatures of < 100 ° C at a level of < 20% by weight. The resulting viscous composition is then foamed at temperatures of > 100 ° C, preferably from 120 to 300 ° C. The residual water still present in the mixture and / or the gaseous products formed in the course of the curing reaction, for example, can act as blowing agents. Otherwise, it is possible to add commercial blowing agents. The polymeric, crosslinked, resulting foams can be used, for example for thermal and acoustic insulation. The compositions of this invention can be used to impregnate paper, which is subsequently dried under mild conditions, to produce laminates, for example for decorative applications, according to known processes. In a second step, these laminates are applied to the substrate to be coated, by lamination with heat and pressure, under chosen conditions so that cure the binder. The compositions of this invention can also be used to produce paper or other abrasives by production techniques commonly practiced with phenolic resin as a binder. In the production of paper sandpapers, a layer of the binders of the invention, as base binders, is first applied (conveniently 10 g / m) to a suitable backing paper. The desired amount of the particulate abrasive is dispersed over the wet base binder. After the initial drying, an upper layer of the binder (for example 5 g / m) is applied. The paper covered in this manner is then cured by heating at 170 ° C for 5 minutes. The hardness and flexibility of the compositions can be set at the desired level by means of the Al polymer composition. The compositions of the invention are also suitable as sand-free formaldehyde binders for cores to produce molds for melt and cores for melting metal in accordance with the conventional processes. The following examples illustrate the invention. The non-volatile fractions were determined in a convection drying oven from the weight loss of a 1 gram sample dried at 120 ° C for 2 hours.

The viscosity of the compositions was determined in a Physica Rheomat at a cutting speed of 250 s_i according to DIN 53019 at 23 ° C. The K value of the polymers A2 was determined in an aqueous solution at 1% concentration. The weighted average particle size of the novel polymers was determined by the quasi-elastic light scattering method. For this, the novel compositions were diluted to a solids content of 0.01% by weight using a 2% solution of sodium lauryl sulfate and measured by means of a Malvern Autosizer 2C.

Example 1: A 4 liter glass vessel with anchor stirrer (120 rpm) was charged with 510 g of water, 960 g of a 50% strength by weight aqueous solution of a copolymer composed of 50 parts by weight of units of acrylic acid and 50 parts by weight of maleic acid units (pH = 0.8, K value = 12) and 300 g of a 40% strength aqueous solution of ethoxylated oleylmonoamine (average degree of ethoxylation = 12). At an internal temperature of 85 ° C, 5% by weight of the total amount of a feed stream 1 and 10% by weight of the total amount of a feed stream 2 were added.

The reaction mixture was initially polymerized at 85 ° C for 10 minutes. Subsequently, at 85 ° C, the rest of the feed stream 1 was supplied continuously during the course of 3 hours and the rest of the feed stream 2 was supplied continuously during the course of 3.5 hours, the 2 streams of food were kept separate. The polymer thus prepared contains 49.8% non-volatile components and has a pH of 1.6. The particle size is 58 nm.

Current of 400 g of styrenes feeding 1: 360 g of methyl methacrylate 40 g of acetacetoxyethyl methacrylate Current of 200 g of water feed 2 8 g of sodium peroxodisulphate Example 2: Initial charge: 1200 g of water 950 g of Sokalan PM IOS (from BASF), a solution at 50% concentration of a maléido acid copolymer (pH = 2, K value = 10; 300 g Of an aqueous solution at 40% concentration by weight of ethoxylated oleyl monoamine (average degree of ethoxylation = 12; Current of 400 g of styrene feed 1 360 g of methyl methacrylate 40 g of hydroxyethyl acrylate Current of 200 g of water feed 2 8 g of 2,2'-azobis (2-amidinopropane) dihydrochloride Procedure as in Example 1. The resulting composition is adjusted with an aqueous solution of ammonia to 25% by weight of concentration at pH 4.0. It contains 39.4% non-volatile components.

Example 3: Initial charge 420 g of water 960 g of a 50% by weight copolymer solution of Example 1. Current of 400 g of feed water 1 300 g of a 40% aqueous solution of oily concentration by weight ethoxylated onoamine (average degree of ethoxylation = 12) 400 g of styrene 400 g of methyl methacrylate Current of 200 g of water feed 2 8 g of 2,2'-azobis (2-amidinopropane) dihydrochloride The cone process in Example 1. In this case the feed stream 1, which is an emulsion, was stirred continuously at 100 rpm. The polymer thus prepared contains 45.4% non-volatile components and has a pH of 1.9. The particle size is 142 nm.

Example 4: Initial charge: 10 g of water 960 g of the 50% strength by weight aqueous copolymer solution of Example 1 300 g of a 40% strength aqueous solution of ethoxylated oleyl mononane (average degree of ethoxylation) = 12) Current of 400 g of styrene feed 1 360 g of methyl methacrylate 40 g of hydroxyethyl acrylate Current of 200 g of water feed 2 8 g of sodium peroxodisulphate Procedure as in Example 1. The polymer thus prepared contains 59.9% non-volatile components and has a pH of 1.5. The particle size is 112 nm Example 5: To 1000 g of the polymer dispersion of Example 4 was added, at room temperature and with stirring, a mixture of 60 g of triethanolamine and 60 g of water. The mixture thus prepared contains 58.8% non-volatile components and has a pH of 3.4.

Example 6: Initial charge 1260 g of water 960 g of an aqueous solution of the copolymer of Example 1 at 50% by weight concentration 300 g of a 40% aqueous solution by weight of ethoxylated oleylmonoamine (average degree of ethoxylation = 12 ) Current of 600 g of styrene feed 1 200 g of methyl methacrylate 40 g of hydroxyethyl acrylate Current of 200 g of water feed 2 8 g of 2,2'-azobis (2-amidinopropane) dihydrochloride Procedure as in Example 1. The polymer thus prepared contains 40.3% non-volatile components. It has a pH of 1.6 and a viscosity of 120 mPas. The particle size is 75 nm.

Example 7: Initial charge: 1200 g of water 960 g of an aqueous solution of the copolymer of Example 1 at 50% concentration by weight 300 g of a 40% strength aqueous solution of ethoxylated oleylmonoamine (average degree of ethoxylation = 12) Current of 400 g of n-butyl acrylate feed 1 76 g of styrene 24 g of methacrylic acid Current of 200 g of water feed 2 8 g of sodium peroxodisulfate Procedure as in Example 1. The polymer thus prepared contains 40.2% of components non-volatile and has a pH of 1.8 and a viscosity of 140 mPas. The particle size is 64 nm.

Example 8: To 1000 g of the polymer dispersion of Example 7 was added, at room temperature and with stirring, a mixture of 63 g of a 77% strength aqueous solution of ethoxylated diethylenetriamine (average degree of ethoxylation = 4.6) and 50 g of water. The mixture thus prepared contains 45.4% non-volatile components and has a pH of 3.1.

Example 9: Initial load. 790 g of water 960 g of a 50% strength by weight solution of polyacrylic acid (pH = 1.2, K = 80) 200 of a 40% aqueous solution by weight of ethoxylated oleylmonoamine (average degree of ethoxylation = 12) Current of 240 g of styrene feed 1 560 g of ethyl acrylate Current of 200 g of water feed 2 8 g of 2,2 'azobis (2-amidinopropane) dihydrochloride Procedure as in Example 1. The polymer thus prepared contains 39.3% non-volatile components and has a pH of 2.2 and a viscosity of 920 mPas. The particle size is 269 nm.

Example 10: Initial charge 300 g of water 13 mg of iron (II) sulphate 7 g of mercaptoethanol Current of 235 g of acrylic acid feed 1 Current of 50 g of feed water 2 12 g, of an aqueous solution of hydrogen peroxide at 30 'of concentration in weight The feed currents 1 and 2 were dosed simultaneously during the course of 1.5 hours at 60 ° C.

After the end of the feeds, stirring was continued at 60 ° C for 1 hour. To the polymer solution thus prepared (K value = 27) was added 880 g of water 75 of a 40% strength aqueous solution of ethoxylated oleylmonoamine (average degree of ethoxylation = 12) This mixture was heated to 85 ° C. Then, at an internal temperature of 85 ° C, 5% by weight of the total amount of a feed stream 3 and 10% by weight of the total amount of a feed stream 4 were added. The reaction mixture was initially polymerized at 85 ° C for 10 minutes. Then, at 85 ° C, the rest of the feed stream 3 was supplied continuously during the course of 3 hours, and the rest of the feed stream 4 was supplied continuously during the course of 3.5 hours, keeping separate the 2 feeding currents.

Current of 200 g of styrene feed 3 180 g of methyl methacrylate 560 g of hydroxyethyl acrylate Current of 200 g of water feed 4 g of 2,2'-azobis (2-amidinopropane) dihydrochloride The polymer thus prepared contains 29.4% non-volatile components and has a pH of 1.6.

Example 11: Initial charge: 520 g of water 960 g of the 50% strength by weight aqueous copolymer solution of Example 1 300 g of a 40% aqueous solution by weight of ethoxylated oleylmonoamine (average degree of ethoxylation = 12) Current of 400 g of styrene feed 1 384 g of ethyl acrylate 16 g of Dynasylan MEMO (supplied by Hüls, chemical name 3-methoxyloxy-propyltrimethoxysilane) Current of 200 g of water feed 2 8 g of 2,2'-azobis (2-amidinopropane) dihydrochloride Procedure as in Example 1. The polymer thus prepared contains 48.9% non-volatile components and has a pH of 1.7.

Comparative Example VI (Composition without polymer 2) Initial charge: 520 g of water 300 g of an aqueous solution at 40, of concentration by weight of ethoxylated oleylmonoamine (average degree of ethoxylation = 12) 10 g of 85% aqueous phosphoric acid of concentration in weight Current of 400 g of styrene feed 1: 360 g of methyl methacrylate 40 g of hydroxyethyl acrylate Current of 200 g of water feed 2: 8 g of 2,2'-azobis (2-amidinopropane) dihydrochloride Procedure as in Example 1. The polymer thus prepared contains 49.5% non-volatile components and has a pH of 4.0 and a particle size of 77 nm.

Comparative Example V2 (Composition without long chain amine) Initial charge: 580 g of water 960 g of the aqueous solution of the copolymer of Example 1 at 50% concentration by weight Current of 400 g of styrene feed 1 360 g of ethyl acrylate 40 g of hydroxyethyl acrylate Current of 200 g of water feed 2 8 g of 2,2 'dihydrochloride azobis (2-amidinopropane) Procedure as in Example 1. During the course of the polymerization there was a severe clot formation, no stable polymer dispersion was obtained.

Comparative Example V3 (according to US 4,868,016 Initial charge: 1215 g of water 45 g of 50% strength by weight solution of polyacrylic acid (pH = 1.2, K = 80) 75 g of a 40% aqueous solution of weight concentration of ethoxylated oleylmonoamine (average degree of ethoxylation = 12) Current of 340 g of methyl methacrylate feed 1 260 g of butyl acrylate 3 g of methacrylic acid Current of 200 g of water feed 2: 6 g of sodium peroxodisulfate Procedure as in Example 1. During the polymerization there was severe clot formation. It was not possible to prepare a stable polymer dispersion.

A) Test as a binder for natural fiber mats.

The binders of the indicated Examples are diluted by adding water to a non-volatile content of 25%. A fiber mat composed of a 1: 1 mixture of jute and henequen fibers (average basis weight 1200 g / m2, residual moisture content 7%, manufactured by Braunschweiger Jute- and Flachs Industriebetriebs-GmbH) are impregnated using a roller foulard with the binder liquor at 25% concentration so that, based on the weight of the dry fiber, apply 25% by weight of non-volatile binder components. The impregnated fiber mats (35 x 30 cm) are dried in a convection drying oven at 80 ° C to a residual moisture content of 10%, based on the dry fibers, and compressed using a hydraulic press to a temperature of 200 ° C and a pressure of 1.5 N / mm2 for two minutes. Flexural strength (RF) is measured using a three-point flexural test according to DIN 52352 at different temperatures (23, 60 and 100 ° C).

The thickness swelling (HE) is determined as the relative increase in thickness of 2 x 2 cm sections of the compressed fiber mats after storage in water at 23 ° C for 2 hours or 24 hours, respectively. Climatic stability: 3 x 10 cm sections of the compressed fiber mats are stored in a controlled climate (CC) drawer at 80 ° C and 90% relative humidity for 1 day or 7 days, respectively. The resistance and decrease in the strength of the test samples is then evaluated related to each other by classifications (classification 1 = very high resistance up to classification 5 = very low resistance) B) Test as binder for cork chips: In a cylindrical mixer, 2.5 g of a binder composition of 46.5% concentration of Example 8 were added to 15 g of cork chips (density density 65 g / 1, average size: 2 mm). The cork chips impregnated with the binder were compressed in a 15 x 15 cm mold at 190 ° C under a pressure of 1.5 N / mm "for 3 minutes to form sheets with a thickness of 2 mm. Leaf after storage in water for 24 hours was 50% and its swelling thickness was 12%.

C) Test as a binder for finely divided mineral materials and for mineral fibers and glass fibers 300g of quartz sand H34 were mixed at room temperature with the binder composition (5% by weight of the dry binder, based on the sand) . The wet mixture was formed in a test sample (bar Fischer) measuring 17 x 2.3 x 2.3 cm and cured at 125 ° C for 2 hours. The flexural strength of the Fischer rods thus produced is determined in the dry state at 23 ° C, 60 and 100 ° C in a PFG resistance tester with the PBV test apparatus (by Georg Fischer, Schaffhausen / CH) . Another Fischer bar is stored for 1 hour in distilled water at 23 ° C. The flexural strength is determined in the humid state at 23 ° C.

D) Testing as coating The compositions were diluted to a non-volatile content of 45% and knife-cut on a glass plate in a wet film thickness of 200 microns. The film was dried at room temperature for 24 hours. The samples were then cured in a drying cabinet at temperatures and during set times. The hardness of the pendulum was determined by the Konig method (DIN 53157) using an instrument for hardness of Pendulum Labotron 5852 by Byk Mallinckrodt GmbH.

Claims (22)

1. A thermosetting aqueous composition containing at least one polymer (Al), containing from 0 to 5% by weight of a α, β-ethylenically unsaturated mono- or dicarboxylic acid in copolymerized form and which is obtained by free radical polymerization in the presence of of: a) at least one polymer (A2) obtainable by free radical polymerization and containing from 15 to 1001 by weight of a mono- or dicarboxylic acid a, β-ethylenically unsaturated in copolymerized form, and b) at least one amine which contains at least one long chain having at least 6 carbons, the weight ratio (based on solids). from the polymer (Al) to the polymer (A2) being from 7: 1 to 1: 7 and that of the polymer (A2) to the long chain amine being from 20: 1 2: 1.

2. The composition as recited in claim 1, wherein the polymer (Al) contains in copolymerized form an α, β-ethylenically unsaturated C3-C6 mono- or dicarboxylic acid, especially acrylic or methacrylic acid.

3. The composition as recited in claim 1 or 2, wherein the polymer (Al) contains in copolymerized form as the main monomer an ester of acrylic or methacrylic acid with an alkanol of C _.- C_.2, a vinylaromatic compound, a vinyl ester of a monocarboxylic acid of C-C12, or an alkyl of C? -C_.2 vinyl ether. The composition as mentioned in any of the preceding claims, wherein the polymer (A2) contains in copolymerized form from 20 to 100% by weight, in particular from 40 to 100% by weight of the mono- or dicarboxylic acid. The composition as mentioned in any of the preceding claims, wherein the polymer (A2) contains in copolymerized form as mono- or dicarboxylic acid at least one compound selected from acrylic, methacrylic, crotonic, fumaric, maleic, 2-methylmalic acid and itaconic. The composition as mentioned in any of the preceding claims, wherein the polymer (A2) contains in a copolymerized form other ethylenically unsaturated monomers selected from the esters of (meth) acrylic acid with monoalcohols of C _.- C_.2, or dialcohols, vinylaromatic compounds, butadiene, vinyl esters. of C2-C12 monocarboxylic acids, aliphatic, C_2-C_2 vinyl ethers, (meth) acrylonitrile, (meth) acrylamide, N-C6-alkyl (meth) acrylamides and N, -di-C3 alkyl -C6 (meth) acrylamides. 7. The composition as recited in any of the preceding claims, wherein the long chain amine is selected from compounds of the formula: RXNRYR2 Where Rx is C6-C22 alkyl, C6-C22 alkenyl, C6-C22 arylalkyl or C6-C22 arylalkenyl and the alkenyl may have from 1 to 3 double bonds, R? and Rz, which may be the same or different, are H, (CH2CH20) nH, where n is from 1 to 25, or Ci-C alkyl. or C5-C7 cycloalkyl which is unsubstituted or substituted by at least one hydroxyl, or are as defined for Rx or together are a 5-6 membered ring which may contain at least one other heteroatom selected from O, N and S 8. The composition as recited in claim 7, wherein Rx is C6-C22 alkyl or C6-C22 alkenyl and Ry and Rz are the same or different and are H or (CH2CH20) pH. The composition as mentioned in any of the preceding claims, which also contains at least one alkanolamine with at least 2 hydroxyls. The composition as recited in claim 9, wherein the alkanolamine is selected from diethanolamine, triethanolamine 'and water-soluble linear or branched aliphatic compounds, which contain per molecule at least two amino functional groups of the type (a) or ( b) (a) < b) where R is hydroxyalkyl and R 'is alkyl. The composition as recited in claim 10, wherein the alkanolamine employed comprises at least one compound of the formula I where A is C2-C? alkylene which is unsubstituted or substituted by one or more groups independently selected from alkyl, hydroxyalkyl, cycloalkyl, OH and NR6R7, where R6 and R7 are independently H, hydroxyalkyl or alkyl, and is uninterrupted or interrupted by one or more oxygens and / or NR5 groups, where R5 is H, hydroxyalkyl, (CH2) mNRdR7, where n is from 2 to 5 and R6 and R7 are as defined above, or alkyl, which in turn may be interrupted by one or more NR5 groups, where R5 is as defined above and / or may be substituted by one or more NR6R7 groups, where R6 and R7 are as defined above, and R ~, R2 and R3 and R4 independently are H, hydroxyalkyl, alkenyl or cyclalkyl. The composition as recited in claim 11, wherein the alkanolamine is selected from at least one compound of the formula la: where Ai is C2-C2 alkylene which is unsubstituted or substituted by at least one alkyl and / or at least NRdR7 group, where R6 and R7 are independently alkyl or hydroxyalkyl, and R1, R2, R3 and R4 independently are hydroxyalkyl or H, or one of R1 and R2 and / or one of R3 and R4 is alkyl or cycloalkyl. The composition as recited in claim 11, wherein the alkanolamine is selected from at least one compound of the formula Ib: where A2 is C2-Ca alkylene which is interrupted by at least one NR5 group, where R5 (or each R5 independently) is hydroxyalogyl or alkyl, and R1, R2, R3 and R4 independently are hydroxyalkyl or H. 1

4. The composition as it is mentioned in claim 11, wherein the alkanolamine is selected from at least one compound of the formula le: where A3 is alkylene of C _-Ce which is interrupted by at least one group NR5 where R5 is H, hydroxyalkyl or CH2CHNRR7, R1, R2, R3 and R4 independently are alkyl which is uninterrupted or interrupted by at least one group NR5 and / or unsubstituted or substituted by at least one group NRdR7, R5 is H, hydroxyalkyl or -R8NR6R7, R6 and R7 independently are H, hydroxyalkyl or -R8NR6R7, and R8 is an ethylene or propylene radical, and where (on average) at least 30% of the nitrogens carry a hydroxyalkyl. 1

5. The composition as recited in claim 14, wherein the alkanolamine is a reaction product of a polyethylenimine with ethylene oxide. 1

6. The composition as recited in any of claims 9 to 15, wherein the hydroxyaluyl group of the alkanolamine in the above definitions is hydroxypropyl or hydroxyethyl. The composition as mentioned in any of the preceding claims, wherein the weight ratio of the polymer (A2) to the alkanolamine is from 100: 1 to 1: 1. 18. The composition as mentioned in any of the previous claims which also contains a reaction accelerator. 19. A binder consisting of a composition as recited in any of claims 1 to 18. 20. A shaped article obtainable by impregnation of a substrate with a composition as recited in any of claims 1 to 18 or with a binder. as mentioned in claim 19 and curing the impregnated substrate. 21. The article formed as claimed in claim 20, which is a sheet or molded part formed from finely divided materials, especially chip board and fiber board, an inner liner for car, an insulating material or a material continuous fiber. 22. The use of an aqueous, heat-curable composition as recited in any of claims 1 to 18 as a binder for formed articles, formed • from finely divided materials, especially of fibers, chips or flakes.